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WO2017030283A1 - Organic electroluminescent compounds and organic electroluminescent device comprising the same - Google Patents

Organic electroluminescent compounds and organic electroluminescent device comprising the same Download PDF

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Publication number
WO2017030283A1
WO2017030283A1 PCT/KR2016/006853 KR2016006853W WO2017030283A1 WO 2017030283 A1 WO2017030283 A1 WO 2017030283A1 KR 2016006853 W KR2016006853 W KR 2016006853W WO 2017030283 A1 WO2017030283 A1 WO 2017030283A1
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substituted
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compound
organic electroluminescent
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French (fr)
Inventor
Hee-Choon Ahn
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DuPont Specialty Materials Korea Ltd
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Rohm and Haas Electronic Materials Korea Ltd
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Priority claimed from KR1020160077395A external-priority patent/KR102112786B1/en
Application filed by Rohm and Haas Electronic Materials Korea Ltd filed Critical Rohm and Haas Electronic Materials Korea Ltd
Priority to JP2018506414A priority Critical patent/JP6788662B2/en
Priority to US15/744,884 priority patent/US20180208837A1/en
Priority to CN201680046295.3A priority patent/CN107922351B/en
Priority to EP16837225.8A priority patent/EP3344606B1/en
Publication of WO2017030283A1 publication Critical patent/WO2017030283A1/en
Anticipated expiration legal-status Critical
Priority to US17/558,910 priority patent/US11807788B2/en
Priority to US18/475,585 priority patent/US12391875B2/en
Ceased legal-status Critical Current

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    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
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    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers

Definitions

  • the present disclosure relates to organic electroluminescent compounds and an organic electroluminescent device comprising the same.
  • An electroluminescent device is a self-light-emitting device which has advantages in that it provides a wider viewing angle, a greater contrast ratio, and a faster response time.
  • the first organic EL device was developed by Eastman Kodak, by using small aromatic diamine molecules, and aluminum complexes as materials for forming a light-emitting layer [Appl. Phys. Lett. 51, 913, 1987].
  • An organic EL device is a device changing electrical energy to light by applying electricity to an organic electroluminescent material, and generally has a structure comprising an anode, a cathode, and an organic layer between the anode and the cathode.
  • the organic layer of an organic EL device may be comprised of a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer (which comprises host and dopant materials), an electron buffer layer, a hole blocking layer, an electron transport layer, an electron injection layer, etc., and the materials used for the organic layer are categorized by their functions in hole injection material, hole transport material, electron blocking material, light-emitting material, electron buffer material, hole blocking material, electron transport material, electron injection material, etc.
  • organic luminescent compounds In the organic EL device, due to an application of a voltage, holes are injected from the anode to the light-emitting layer, electrons are injected from the cathode to the light-emitting layer, and excitons of high energies are formed by a recombination of the holes and the electrons. By this energy, organic luminescent compounds reach an excited state, and light emission occurs by emitting light from energy due to the excited state of the organic luminescent compounds returning to a ground state.
  • a light-emitting material must have high quantum efficiency, and high electron and hole mobility, and the formed light-emitting material layer must be uniform and stable.
  • Light-emitting materials are categorized into blue, green, and red light-emitting materials dependent on the color of the light emission, and additionally yellow or orange light-emitting materials.
  • light-emitting materials can also be categorized into host and dopant materials according to their functions.
  • the host material which acts as a solvent in a solid state and transfers energy, needs to have high purity and a molecular weight appropriate for vacuum deposition. Furthermore, the host material needs to have high glass transition temperature and high thermal degradation temperature to achieve thermal stability, high electro-chemical stability to achieve a long lifespan, ease of forming an amorphous thin film, good adhesion to materials of adjacent layers, and non-migration to other layers.
  • the electron buffer layer can improve the problem that when exposed to a high temperature in the process of the manufacture of panels, the current properties of the device may be changed in the devices, thereby lowering the light-emitting luminance, and thus the properties of compounds comprised in the electron buffer layer are important.
  • Japanese patent application laid-open No. 2001-23777 discloses an organic electroluminescent device using a phenanthrene compound, in which a 5-membered heteroaryl containing nitrogen is condensed with the middle benzene ring of the phenanthrene backbone, as a host material.
  • the organic electroluminescent device comprising the compound disclosed in Japanese patent application laid-open No. 2001-23777 shows excellent color purity characteristics of blue, but needs for improving driving voltage, current efficiency, and operative lifespan of the organic electroluminescent device have still remained.
  • the present inventors have found that low driving voltage, excellent efficiency, and a significantly improved operative lifespan of an organic electroluminescent device could be achieved by using a phenanthrene compound, in which a 5-membered heteroaryl is condensed with a side benzene ring of the phenanthrene backbone, as a host or in the electron buffer layer.
  • the object of the present disclosure is to provide organic electroluminescent compounds being effective to produce an organic electroluminescent device having low driving voltage, excellent current and power efficiencies, and significantly improved operative lifespan.
  • R 1 represents a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered)heteroaryl;
  • R 2 to R 4 , R 7 , and R 8 each independently, represent hydrogen, deuterium, a halogen, a cyano, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (3- to 30-membered)heteroaryl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C1-C30)alkoxy, a substituted or unsubstituted tri(C1-C30)alkylsilyl, a substituted or unsubstituted di(C1-C30)alkyl(C6-C30)arylsilyl, a substituted or unsubstituted (C1-C30)alkyldi(C6-C30)arylsilyl, a substituted or unsub
  • the heteroaryl contains at least one heteroatom selected from B, N, O, S, Si, and P.
  • the organic electroluminescent compound of the present disclosure By using the organic electroluminescent compound of the present disclosure in a light-emitting layer as a host or in an electron buffer layer, efficiency, and lifespan of the organic electroluminescent device are significantly improved compared to the conventional organic electroluminescent compounds.
  • the organic electroluminescent compound of the present disclosure shows properties more suitable to the current trend of increasing demand for high resolution by maintaining high efficiency at high luminance and having a significantly improved lifespan.
  • the present disclosure relates to an organic electroluminescent compound represented by formula 1, an organic electroluminescent material comprising the organic electroluminescent compound, and an organic electroluminescent device comprising the organic electroluminescent compound.
  • the organic electroluminescent compound of formula 1 may be represented by any one of the following formulae 2 to 4:
  • R 1 represents a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered)heteroaryl; preferably, a substituted or unsubstituted (C6-C30)aryl, or a substituted (5- to 25-membered)heteroaryl; and more preferably, a substituted or unsubstituted (C6-C30)aryl, or a substituted (5- to 20-membered)heteroaryl.
  • R 1 may be an unsubstituted phenyl, an unsubstituted biphenyl, an unsubstituted naphthyl, a fluorenyl substituted with methyl, a benzofluorenyl substituted with methyl, a carbazolyl substituted with phenyl, a benzocarbazolyl substituted with phenyl, an indolocarbazolyl substituted with phenyl, an unsubstituted dibenzofuranyl, an unsubstituted dibenzothiophenyl, a spiro[fluorene-fluorene], or a spiro[fluorene-benzofluorene].
  • R 2 to R 9 each independently, represent hydrogen, deuterium, a halogen, a cyano, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (3- to 30-membered)heteroaryl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C1-C30)alkoxy, a substituted or unsubstituted tri(C1-C30)alkylsilyl, a substituted or unsubstituted di(C1-C30)alkyl(C6-C30)arylsilyl, a substituted or unsubstituted (C1-C30)alkyldi(C6-C30)arylsilyl, a substituted or unsubstit
  • R 2 to R 4 may be selected from the group consisting of hydrogen, a substituted phenyl, a substituted triazinyl, a substituted pyrimidinyl, a substituted or unsubstituted carbazolyl, a substituted benzocarbazolyl, an unsubstituted dibenzocarbazolyl, and a substituted or unsubstituted diphenylamino, or may be linked to an adjacent substituent(s) to form a substituted indene ring, or a substituted benzothiophene ring.
  • R 5 and R 6 each independently, may be selected from the group consisting of hydrogen, a substituted or unsubstituted phenyl, a substituted or unsubstituted carbazolyl, an unsubstituted benzocarbazolyl, and an unsubstituted dibenzocarbazolyl, or may be linked to an adjacent substituent(s) to form an unsubstituted benzene ring, an indole ring substituted with phenyl, a benzoindole ring substituted with phenyl, an indene ring substituted with methyl, or a benzoindene ring substituted with methyl.
  • R 7 and R 8 may be a substituted phenyl.
  • a represents 1; and b and c, each independently, represent 1 or 2, preferably 1.
  • d represents an integer of 1 to 4, preferably 1 or 2.
  • L 1 represents a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (3- to 30-membered)heteroarylene; preferably, a single bond, or a substituted or unsubstituted (C6-C18)arylene; more preferably, a single bond, or an unsubstituted (C6-C12)arylene; and for example, a single bond, or an unsubstituted phenyl.
  • X 2 to X 4 each independently, represent -N- or -CR 9 -; preferably, at least one of X 2 to X 4 represents -N-; and more preferably, at least two of X 2 to X 4 represent -N-.
  • R 9 may be hydrogen.
  • Ar 1 and Ar 2 each independently, represent a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered)heteroaryl; preferably, a substituted or unsubstituted (C6-C25)aryl, or a substituted or unsubstituted (3- to 25-membered)heteroaryl; more preferably, an unsubstituted (C6-C20)aryl, or a substituted or unsubstituted (5- to 20-membered)heteroaryl; and for example, an unsubstituted phenyl, an unsubstituted biphenyl, an unsubstiuted naphthyl, an unsubstituted dibenzothiophenyl, a fluorenyl substituted with methyl, a benzofluorenyl substituted with methyl, a carbazolyl substituted with phen
  • e represents an integer of 1 to 3, preferably 1 or 2.
  • Z represents a single bond, or a substituted or unsubstituted (C1-C6)alkylene; and preferably, a single bond.
  • n 0 or 1; and f and g, each independently, represent an integer of 1 to 4, preferably 1 or 2.
  • W represents -NR 10 -, -O-, -S-, or -CR 11 R 12 -, preferably -NR 10 -.
  • R 10 represents a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered)heteroaryl; preferably, a substituted or unsubstituted (C6-C20)aryl; more preferably, an unsubstituted (C6-C18)aryl; and for example, an unsubstituted phenyl.
  • R 11 and R 12 each independently, represent a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered)heteroaryl; preferably, each independently, represent a substituted or unsubstituted (C1-C20)alkyl; more preferably, each independently, represent an unsubstituted (C1-C15)alkyl; and for example, an unsubstituted methyl.
  • (C1-C30)alkyl is meant to be a linear or branched alkyl having 1 to 30 carbon atoms constituting the chain, in which the number of carbon atoms is preferably 1 to 20, more preferably 1 to 10, and includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.; “(C3-C30)cycloalkyl” is a mono- or polycyclic hydrocarbon having 3 to 30 ring backbone carbon atoms, in which the number of carbon atoms is preferably 3 to 20, more preferably 3 to 7, and includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.; “(C6-C30)aryl(ene)” is a monocyclic or fused ring derived from an aromatic hydrocarbon having 6 to 30 ring backbone carbon atoms, in which the number of
  • substituted in the expression “substituted or unsubstituted” means that a hydrogen atom in a certain functional group is replaced with another atom or group, i.e. a substituent.
  • the organic electroluminescent compound represented by formula 1 includes the following compounds, but is not limited thereto:
  • the present disclosure further provides an organic electroluminescent material comprising the organic electroluminescent compound of formula 1, and an organic electroluminescent device comprising the organic electroluminescent material.
  • the organic electroluminescent material can be comprised of the organic electroluminescent compound of the present disclosure alone, or can further include conventional materials generally used in organic electroluminescent materials.
  • the organic electroluminescent device of the present disclosure may comprise a first electrode, a second electrode, and at least one organic layer between the first and second electrodes.
  • the organic layer may comprise at least one organic electroluminescent compound of formula 1.
  • the organic layer may comprise a light-emitting layer, and may further comprise at least one layer selected from a hole injection layer, a hole transport layer, an electron transport layer, an electron buffer layer, an electron injection layer, an interlayer, a hole blocking layer, and an electron blocking layer.
  • the organic electroluminescent compound of formula 1 of the present disclosure can be comprised in the light-emitting layer as a host material or in an electron buffer layer.
  • the light-emitting layer may comprise at least one dopant.
  • another compound besides the organic electroluminescent compound of formula 1 may be comprised as a second host material.
  • Another embodiment of the present disclosure provides an electron buffer material comprising the organic electroluminescent compound of formula 1, and an organic electroluminescent device comprising the electron buffer material.
  • the organic electroluminescent device of the present disclosure comprises a first electrode; a second electrode opposing the first electrode; a light-emitting layer between the first electrode and the second electrode; and an electron transport zone and an electron buffer layer between the light-emitting layer and the second electrode.
  • the electron buffer layer may comprise a compound represented by formula 1.
  • the dopant used in the present disclosure is preferably at least one phosphorescent dopant.
  • the phosphorescent dopant material used for the organic electroluminescent device of the present disclosure is not limited, but may be preferably selected from metallated complex compounds of iridium (Ir), osmium (Os), copper (Cu), and platinum (Pt), more preferably selected from ortho-metallated complex compounds of iridium (Ir), osmium (Os), copper (Cu), and platinum (Pt), and even more preferably ortho-metallated iridium complex compounds.
  • the dopant to be comprised in the organic electroluminescent device of the present disclosure may be selected from the group consisting of the compounds represented by the following formulae 10 to 12.
  • L d is selected from the following structures:
  • R 100 represents hydrogen, a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C3-C30)cycloalkyl;
  • R 101 to R 109 and R 111 to R 123 each independently, represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C3-C30)cycloalkyl, a cyano, or a substituted or unsubstituted (C1-C30)alkoxy; and adjacent substituents of R 120 to R 123 may be linked to each other to form a substituted or unsubstituted fused ring, e.g., a substituted or unsubstituted quinoline;
  • R 124 to R 127 each independently, represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C6-C30)aryl; and adjacent substituents of R 124 to R 127 may be linked to each other to form a substituted or unsubstituted fused ring, e.g., a substituted or unsubstituted fluorene, a substituted or unsubstituted dibenzothiophene, or a substituted or unsubstituted dibenzofuran;
  • R 201 to R 211 each independently, represent hydrogen, deuterium, a halogen, a substituted or unsubstituted a (C1-C30)alkyl, a substituted or unsubstituted (C3-C30)cycloalkyl, or a substituted or unsubstituted (C6-C30)aryl; and adjacent substituents of R 201 to R 211 may be linked to each other to form a substituted or unsubstituted fused ring, e.g., a substituted or unsubstituted dibenzofuran, or a substituted or unsubstituted dibenzothiophene;
  • r and s each independently, represent an integer of 1 to 3; where r or s is an integer of 2 or more, each of R 100 may be the same or different; and
  • t represents an integer of 1 to 3.
  • the phosphorescent dopant materials include the following:
  • the organic electroluminescent device of the present disclosure may further comprise, in addition to the compound of formula 1, at least one compound selected from the group consisting of arylamine-based compounds and styrylarylamine-based compounds.
  • the organic layer may further comprise, in addition to the compound of formula 1, at least one metal selected from the group consisting of metals of Group 1, metals of Group 2, transition metals of the 4 th period, transition metals of the 5 th period, lanthanides, and organic metals of the d-transition elements of the Periodic Table, or at least one complex compound comprising the metal.
  • the organic layer may further comprise one or more additional light-emitting layers and a charge generating layer.
  • the organic electroluminescent device of the present disclosure may emit white light by further comprising at least one light-emitting layer, which comprises a blue, a red, or a green electroluminescent compound known in the field, besides the compound of the present disclosure. If necessary, it may further comprise a yellow or an orange light-emitting layer.
  • a surface layer may be placed on an inner surface(s) of one or both electrode(s), selected from a chalcogenide layer, a metal halide layer, and a metal oxide layer.
  • a chalcogenide (includes oxides) layer of silicon or aluminum is preferably placed on an anode surface of an electroluminescent medium layer
  • a metal halide layer or a metal oxide layer is preferably placed on a cathode surface of an electroluminescent medium layer.
  • the chalcogenide includes SiO X (1 ⁇ X ⁇ 2), AlO X (1 ⁇ X ⁇ 1.5), SiON, SiAlON, etc.;
  • the metal halide includes LiF, MgF 2 , CaF 2 , a rare earth metal fluoride, etc.; and the metal oxide includes Cs 2 O, Li 2 O, MgO, SrO, BaO, CaO, etc.
  • a mixed region of an electron transport compound and a reductive dopant, or a mixed region of a hole transport compound and an oxidative dopant may be placed on at least one surface of a pair of electrodes.
  • the electron transport compound is reduced to an anion, and thus it becomes easier to inject and transport electrons from the mixed region to an electroluminescent medium.
  • the hole transport compound is oxidized to a cation, and thus it becomes easier to inject and transport holes from the mixed region to the electroluminescent medium.
  • the oxidative dopant includes various Lewis acids and acceptor compounds
  • the reductive dopant includes alkali metals, alkali metal compounds, alkaline earth metals, rare-earth metals, and mixtures thereof.
  • a reductive dopant layer may be employed as a charge generating layer to prepare an electroluminescent device having two or more light-emitting layers and emitting white light.
  • dry film-forming methods such as vacuum evaporation, sputtering, plasma, and ion plating methods, or wet film-forming methods such as ink jet printing, nozzle printing, slot coating, spin coating, dip coating, and flow coating methods can be used.
  • a thin film can be formed by dissolving or diffusing materials forming each layer into any suitable solvent such as ethanol, chloroform, tetrahydrofuran, dioxane, etc.
  • the solvent can be any solvent where the materials forming each layer can be dissolved or diffused, and where there are no problems in film-formation capability.
  • organic electroluminescent compounds of the present disclosure the preparation method thereof, and the properties of the device comprising the compounds will be explained in detail with reference to the representative compounds of the present disclosure.
  • Compound G was prepared in the same manner as the preparation of compound 3-2 described in Example 4, except for using 5-chloro-2-formylboronic acid instead of 4-chloro-2-formylbenzene boronic acid.
  • electroluminescent compounds of the present disclosure as a host
  • An OLED device was produced by using the organic electroluminescent compound according to the present disclosure.
  • a transparent electrode indium tin oxide (ITO) thin film (10 ⁇ /sq) on a glass substrate for an organic light-emitting diode (OLED) device (Geomatec) was subjected to an ultrasonic washing with acetone, ethanol, and distilled water, sequentially, and then was stored in isopropanol.
  • the ITO substrate was then mounted on a substrate holder of a vacuum vapor depositing apparatus.
  • Compound HI-1 was introduced into a cell of said vacuum vapor depositing apparatus, and then the pressure in the chamber of said apparatus was controlled to 10 -6 torr.
  • compound HI-2 was introduced into another cell of said vacuum vapor depositing apparatus, and was evaporated by applying an electric current to the cell, thereby forming a second hole injection layer having a thickness of 5 nm on the first hole injection layer.
  • Compound HT-1 was then introduced into the cell of said vacuum vapor depositing apparatus, and was evaporated by applying an electric current to the cell, thereby forming a first hole transport layer having a thickness of 10 nm on the second hole injection layer.
  • Compound HT-3 was then introduced into another cell of said vacuum vapor depositing apparatus, and was evaporated by applying an electric current to the cell, thereby forming a second hole transport layer having a thickness of 60 nm on the first hole transport layer.
  • a light-emitting layer was formed thereon as follows: compound C-24 was introduced into one cell of said vacuum vapor depositing apparatus as a host, and compound D-71 was introduced into another cell as a dopant. The dopant was deposited in a doping amount of 3 wt% based on the total amount of the host and dopant to form a light-emitting layer having a thickness of 40 nm on the second hole transport layer.
  • Compound ET-1 and compound EI-1 were then introduced into another two cells, and evaporated at a rate of 1:1 to form an electron transport layer having a thickness of 30 nm on the light-emitting layer.
  • an Al cathode having a thickness of 80 nm was deposited by another vacuum vapor deposition apparatus. Thus, an OLED device was produced.
  • the produced OLED device showed a red emission having a luminance of 1,000 cd/m 2 , and a luminous efficiency of 24.4 cd/A at 4.4 V.
  • the time taken to be reduced to 90% of the luminance, where the early luminance is 100%, at 5,000 nits and a constant current was 43 hours or more.
  • electroluminescent compounds of the present disclosure as a host
  • An OLED device was produced in the same manner as in Device Example 1, except for using compound C-1 as a host of the light-emitting material.
  • the produced OLED device showed a red emission having a luminance of 1,000 cd/m 2 , and a luminous efficiency of 27.8 cd/A at 6.0 V.
  • the time taken to be reduced to 90% of the luminance, where the early luminance is 100%, at 5,000 nits and a constant current was 37 hours or more.
  • electroluminescent compounds of the present disclosure as a host
  • An OLED device was produced in the same manner as in Device Example 1, except for using the compound C-39 as a host of the light-emitting material.
  • the produced OLED device showed a red emission having a luminance of 1,000 cd/m 2 , and a luminous efficiency of 22.9 cd/A at 4.5 V.
  • the time taken to be reduced to 90% of the luminance, where the early luminance is 100%, at 5,000 nits and a constant current was 38 hours or more.
  • Comparative Device Example 1 Preparation of an OLED device comprising
  • An OLED device was produced in the same manner as in Device Example 1, except for using the following compound K as a host of the light-emitting material.
  • the produced OLED device showed a red emission having a luminance of 1,000 cd/m 2 , and a luminous efficiency of 14.3 cd/A at 10.0 V.
  • the time taken to be reduced to 90% of the luminance, where the early luminance is 100%, at 5,000 nits and a constant current was less than 1 hour.

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Abstract

The present disclosure relates to organic electroluminescent compounds and an organic electroluminescent device comprising the same. The organic electroluminescent compound according to the present disclosure may be comprised in a light-emitting layer or an electron buffer layer, and is effective to produce an organic electroluminescent device having low driving voltage, excellent current and power efficiencies, and significantly improved operative lifespan.

Description

ORGANIC ELECTROLUMINESCENT COMPOUNDS AND ORGANIC ELECTROLUMINESCENT DEVICE COMPRISING THE SAME
The present disclosure relates to organic electroluminescent compounds and an organic electroluminescent device comprising the same.
An electroluminescent device (EL device) is a self-light-emitting device which has advantages in that it provides a wider viewing angle, a greater contrast ratio, and a faster response time. The first organic EL device was developed by Eastman Kodak, by using small aromatic diamine molecules, and aluminum complexes as materials for forming a light-emitting layer [Appl. Phys. Lett. 51, 913, 1987].
An organic EL device (OLED) is a device changing electrical energy to light by applying electricity to an organic electroluminescent material, and generally has a structure comprising an anode, a cathode, and an organic layer between the anode and the cathode. The organic layer of an organic EL device may be comprised of a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer (which comprises host and dopant materials), an electron buffer layer, a hole blocking layer, an electron transport layer, an electron injection layer, etc., and the materials used for the organic layer are categorized by their functions in hole injection material, hole transport material, electron blocking material, light-emitting material, electron buffer material, hole blocking material, electron transport material, electron injection material, etc. In the organic EL device, due to an application of a voltage, holes are injected from the anode to the light-emitting layer, electrons are injected from the cathode to the light-emitting layer, and excitons of high energies are formed by a recombination of the holes and the electrons. By this energy, organic luminescent compounds reach an excited state, and light emission occurs by emitting light from energy due to the excited state of the organic luminescent compounds returning to a ground state.
The most important factor determining luminous efficiency in an organic EL device is light-emitting materials. A light-emitting material must have high quantum efficiency, and high electron and hole mobility, and the formed light-emitting material layer must be uniform and stable. Light-emitting materials are categorized into blue, green, and red light-emitting materials dependent on the color of the light emission, and additionally yellow or orange light-emitting materials. In addition, light-emitting materials can also be categorized into host and dopant materials according to their functions. Recently, the development of an organic EL device providing high efficiency and long lifespan is an urgent issue. In particular, considering EL characteristic requirements for a middle or large-sized panel of OLED, materials showing better characteristics than conventional ones must be urgently developed. The host material, which acts as a solvent in a solid state and transfers energy, needs to have high purity and a molecular weight appropriate for vacuum deposition. Furthermore, the host material needs to have high glass transition temperature and high thermal degradation temperature to achieve thermal stability, high electro-chemical stability to achieve a long lifespan, ease of forming an amorphous thin film, good adhesion to materials of adjacent layers, and non-migration to other layers.
Also, the electron buffer layer can improve the problem that when exposed to a high temperature in the process of the manufacture of panels, the current properties of the device may be changed in the devices, thereby lowering the light-emitting luminance, and thus the properties of compounds comprised in the electron buffer layer are important.
Japanese patent application laid-open No. 2001-23777 discloses an organic electroluminescent device using a phenanthrene compound, in which a 5-membered heteroaryl containing nitrogen is condensed with the middle benzene ring of the phenanthrene backbone, as a host material.
The organic electroluminescent device comprising the compound disclosed in Japanese patent application laid-open No. 2001-23777 shows excellent color purity characteristics of blue, but needs for improving driving voltage, current efficiency, and operative lifespan of the organic electroluminescent device have still remained.
In this regard, the present inventors have found that low driving voltage, excellent efficiency, and a significantly improved operative lifespan of an organic electroluminescent device could be achieved by using a phenanthrene compound, in which a 5-membered heteroaryl is condensed with a side benzene ring of the phenanthrene backbone, as a host or in the electron buffer layer.
The object of the present disclosure is to provide organic electroluminescent compounds being effective to produce an organic electroluminescent device having low driving voltage, excellent current and power efficiencies, and significantly improved operative lifespan.
The present inventors found that the above objective can be achieved by an organic electroluminescent compound represented by the following formula 1:
Figure PCTKR2016006853-appb-I000001
wherein
X1 represents -N=, -NR7-, -O-, or -S-;
Y1 represents -N=, -NR8-, -O-, or -S-;
with the provisos that when X1 represents -N=, then Y1 represents -NR8-, -O-, or -S-, and when X1 represents -NR7-, then Y1 represents -N=, -O-, or -S-, with the provisos that X1 and Y1 are not simultaneously -O-; X1 and Y1 are not simultaneously -S-; X1 and Y1 are not -O- and -S-, respectively; and X1 and Y1 are not -S- and -O-, respectively;
R1 represents a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered)heteroaryl;
R2 to R4, R7, and R8, each independently, represent hydrogen, deuterium, a halogen, a cyano, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (3- to 30-membered)heteroaryl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C1-C30)alkoxy, a substituted or unsubstituted tri(C1-C30)alkylsilyl, a substituted or unsubstituted di(C1-C30)alkyl(C6-C30)arylsilyl, a substituted or unsubstituted (C1-C30)alkyldi(C6-C30)arylsilyl, a substituted or unsubstituted tri(C6-C30)arylsilyl, a substituted or unsubstituted mono- or di- (C1-C30)alkylamino, a substituted or unsubstituted mono- or di- (C6-C30)arylamino, or a substituted or unsubstituted (C1-C30)alkyl(C6-C30)arylamino; or are linked to an adjacent substituent(s) to form a substituted or unsubstituted, mono- or polycyclic, (C3-C30) alicyclic or aromatic ring, whose carbon atom(s) may be replaced with at least one heteroatom selected from nitrogen, oxygen, and sulfur;
a represents 1; b and c, each independently, represent 1 or 2; d represents an integer of 1 to 4; and
the heteroaryl contains at least one heteroatom selected from B, N, O, S, Si, and P.
By using the organic electroluminescent compound of the present disclosure in a light-emitting layer as a host or in an electron buffer layer, efficiency, and lifespan of the organic electroluminescent device are significantly improved compared to the conventional organic electroluminescent compounds. In particular, the organic electroluminescent compound of the present disclosure shows properties more suitable to the current trend of increasing demand for high resolution by maintaining high efficiency at high luminance and having a significantly improved lifespan.
Hereinafter, the present disclosure will be described in detail. However, the following description is intended to explain the disclosure, and is not meant in any way to restrict the scope of the disclosure.
The present disclosure relates to an organic electroluminescent compound represented by formula 1, an organic electroluminescent material comprising the organic electroluminescent compound, and an organic electroluminescent device comprising the organic electroluminescent compound.
The organic electroluminescent compound of formula 1 may be represented by any one of the following formulae 2 to 4:
Figure PCTKR2016006853-appb-I000002
Figure PCTKR2016006853-appb-I000003
Figure PCTKR2016006853-appb-I000004
In formulae 1 to 4, R1 represents a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered)heteroaryl; preferably, a substituted or unsubstituted (C6-C30)aryl, or a substituted (5- to 25-membered)heteroaryl; and more preferably, a substituted or unsubstituted (C6-C30)aryl, or a substituted (5- to 20-membered)heteroaryl. For example, R1 may be an unsubstituted phenyl, an unsubstituted biphenyl, an unsubstituted naphthyl, a fluorenyl substituted with methyl, a benzofluorenyl substituted with methyl, a carbazolyl substituted with phenyl, a benzocarbazolyl substituted with phenyl, an indolocarbazolyl substituted with phenyl, an unsubstituted dibenzofuranyl, an unsubstituted dibenzothiophenyl, a spiro[fluorene-fluorene], or a spiro[fluorene-benzofluorene].
In formulae 1 to 4, R2 to R9, each independently, represent hydrogen, deuterium, a halogen, a cyano, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (3- to 30-membered)heteroaryl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C1-C30)alkoxy, a substituted or unsubstituted tri(C1-C30)alkylsilyl, a substituted or unsubstituted di(C1-C30)alkyl(C6-C30)arylsilyl, a substituted or unsubstituted (C1-C30)alkyldi(C6-C30)arylsilyl, a substituted or unsubstituted tri(C6-C30)arylsilyl, a substituted or unsubstituted mono- or di- (C1-C30)alkylamino, a substituted or unsubstituted mono- or di- (C6-C30)arylamino, or a substituted or unsubstituted (C1-C30)alkyl(C6-C30)arylamino; or are linked to an adjacent substituent(s) to form a substituted or unsubstituted, mono- or polycyclic, (C3-C30) alicyclic or aromatic ring, whose carbon atom(s) may be replaced with at least one heteroatom selected from nitrogen, oxygen, and sulfur; preferably, each independently, hydrogen, a substituted or unsubstituted (C6-C25)aryl, a substituted or unsubstituted (3- to 25-membered)heteroaryl, or a substituted or unsubstituted mono- or di- (C6-C25)arylamino; or are linked to an adjacent substituent(s) to form a substituted or unsubstituted, mono- or polycyclic, (C3-C25) alicyclic or aromatic ring, whose carbon atom(s) may be replaced with at least one heteroatom selected from nitrogen, oxygen, and sulfur; more preferably, each independently, hydrogen, a substituted or unsubstituted (C6-C20)aryl, a substituted or unsubstituted (5- to 25-membered)heteroaryl, or a substituted or unsubstituted di(C6-C18)arylamino; or are linked to an adjacent substituent(s) to form a substituted or unsubstituted, mono- or polycyclic, (C3-C25) alicyclic or aromatic ring, whose carbon atom(s) may be replaced with at least one heteroatom selected from nitrogen and sulfur; and the heteroaryl contains at least one heteroatom selected from B, N, O, S, Si, and P. For example, R2 to R4, each independently, may be selected from the group consisting of hydrogen, a substituted phenyl, a substituted triazinyl, a substituted pyrimidinyl, a substituted or unsubstituted carbazolyl, a substituted benzocarbazolyl, an unsubstituted dibenzocarbazolyl, and a substituted or unsubstituted diphenylamino, or may be linked to an adjacent substituent(s) to form a substituted indene ring, or a substituted benzothiophene ring. Also, for example, R5 and R6, each independently, may be selected from the group consisting of hydrogen, a substituted or unsubstituted phenyl, a substituted or unsubstituted carbazolyl, an unsubstituted benzocarbazolyl, and an unsubstituted dibenzocarbazolyl, or may be linked to an adjacent substituent(s) to form an unsubstituted benzene ring, an indole ring substituted with phenyl, a benzoindole ring substituted with phenyl, an indene ring substituted with methyl, or a benzoindene ring substituted with methyl.
In formulae 1 to 4, X1 represents -N=, -NR7-, -O-, or -S-; Y1 represents -N=, -NR8-, -O-, or -S-; with the provisos that when X1 represents -N=, then Y1 represents -NR8-, -O-, or -S-, and when X1 represents -NR7-, then Y1 represents -N=, -O-, or -S-, with the provisos that X1 and Y1 are not simultaneously -O-; X1 and Y1 are not simultaneously -S-; X1 and Y1 are not -O- and -S-, respectively; and X1 and Y1 are not -S- and -O-, respectively. Herein, R7 and R8 may be a substituted phenyl.
In formulae 1 to 4, a represents 1; and b and c, each independently, represent 1 or 2, preferably 1.
In formula 1, d represents an integer of 1 to 4, preferably 1 or 2.
In formulae 2 to 4, L1 represents a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (3- to 30-membered)heteroarylene; preferably, a single bond, or a substituted or unsubstituted (C6-C18)arylene; more preferably, a single bond, or an unsubstituted (C6-C12)arylene; and for example, a single bond, or an unsubstituted phenyl.
In formula 2, X2 to X4, each independently, represent -N- or -CR9-; preferably, at least one of X2 to X4 represents -N-; and more preferably, at least two of X2 to X4 represent -N-. Herein, R9 may be hydrogen.
In formula 2, Ar1 and Ar2, each independently, represent a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered)heteroaryl; preferably, a substituted or unsubstituted (C6-C25)aryl, or a substituted or unsubstituted (3- to 25-membered)heteroaryl; more preferably, an unsubstituted (C6-C20)aryl, or a substituted or unsubstituted (5- to 20-membered)heteroaryl; and for example, an unsubstituted phenyl, an unsubstituted biphenyl, an unsubstiuted naphthyl, an unsubstituted dibenzothiophenyl, a fluorenyl substituted with methyl, a benzofluorenyl substituted with methyl, a carbazolyl substituted with phenyl, a benzocarbazolyl substituted with phenyl, or an unsubstituted benzonaphthothiophenyl.
In formulae 2 to 4, e represents an integer of 1 to 3, preferably 1 or 2.
In formulae 3 and 4, Z represents a single bond, or a substituted or unsubstituted (C1-C6)alkylene; and preferably, a single bond.
In formula 3, n represents 0 or 1; and f and g, each independently, represent an integer of 1 to 4, preferably 1 or 2.
In formula 4, n represents 0 or 1, preferably 1; g represents an integer of 1 to 4, preferably 1 or 2; and h represents an integer of 1 to 3, preferably 1 or 2.
In formula 4, W represents -NR10-, -O-, -S-, or -CR11R12-, preferably -NR10-.
In formula 4, R10 represents a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered)heteroaryl; preferably, a substituted or unsubstituted (C6-C20)aryl; more preferably, an unsubstituted (C6-C18)aryl; and for example, an unsubstituted phenyl.
In formula 4, R11 and R12, each independently, represent a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered)heteroaryl; preferably, each independently, represent a substituted or unsubstituted (C1-C20)alkyl; more preferably, each independently, represent an unsubstituted (C1-C15)alkyl; and for example, an unsubstituted methyl.
Herein, “(C1-C30)alkyl” is meant to be a linear or branched alkyl having 1 to 30 carbon atoms constituting the chain, in which the number of carbon atoms is preferably 1 to 20, more preferably 1 to 10, and includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.; “(C3-C30)cycloalkyl” is a mono- or polycyclic hydrocarbon having 3 to 30 ring backbone carbon atoms, in which the number of carbon atoms is preferably 3 to 20, more preferably 3 to 7, and includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.; “(C6-C30)aryl(ene)” is a monocyclic or fused ring derived from an aromatic hydrocarbon having 6 to 30 ring backbone carbon atoms, in which the number of carbon atoms is preferably 6 to 20, more preferably 6 to 15, and includes phenyl, biphenyl, terphenyl, naphthyl, binaphthyl, phenylnaphthyl, naphthylphenyl, fluorenyl, phenylfluorenyl, benzofluorenyl, dibenzofluorenyl, phenanthrenyl, phenylphenanthrenyl, anthracenyl, indenyl, triphenylenyl, pyrenyl, tetracenyl, perylenyl, chrysenyl, naphthacenyl, fluoranthenyl, etc.; and “(3- to 30-membered) heteroaryl(ene)” is an aryl having 3 to 30 ring backbone atoms, preferably 5 to 25 ring backbone atoms, including at least one, preferably 1 to 4 heteroatoms selected from the group consisting of B, N, O, S, Si, and P; may be a monocyclic ring, or a fused ring condensed with at least one benzene ring; may be partially saturated; may be one formed by linking at least one heteroaryl or aryl group to a heteroaryl group via a single bond(s); and includes a monocyclic ring-type heteroaryl including furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, etc., and a fused ring-type heteroaryl including benzofuranyl, benzothiophenyl, isobenzofuranyl, dibenzofuranyl, dibenzothiophenyl, benzimidazolyl, benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, isoindolyl, indolyl, benzoindolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, benzocarbazolyl, dibenzocarbazolyl, phenoxazinyl, phenanthridinyl, benzodioxolyl, etc. Furthermore, “halogen” includes F, Cl, Br, and I.
Herein, “substituted” in the expression “substituted or unsubstituted” means that a hydrogen atom in a certain functional group is replaced with another atom or group, i.e. a substituent. The substituents of the substituted alkyl(ene), the substituted aryl(ene), the substituted heteroaryl(ene), the substituted cycloalkyl, the substituted alkoxy, the substituted trialkylsilyl, the substituted dialkylarylsilyl, the substituted alkyldiarylsilyl, the substituted triarylsilyl, the substituted mono- or di-alkylamino, the substituted mono- or di-arylamino, the substituted alkylarylamino, and the substituted mono- or polycyclic, alicyclic or aromatic ring in R1 to R12, L1, Ar1, Ar2, and Z of formulae 1 to 4, each independently, are at least one selected from the group consisting of deuterium; a halogen; a cyano; a carboxyl; a nitro; a hydroxyl; a (C1-C30)alkyl; a halo(C1-C30)alkyl; a (C2-C30)alkenyl; a (C2-C30)alkynyl; a (C1-C30)alkoxy; a (C1-C30)alkylthio; a (C3-C30)cycloalkyl; a (C3-C30)cycloalkenyl; a (3- to 7-membered)heterocycloalkyl; a (C6-C30)aryloxy; a (C6-C30)arylthio; a (3- to 30-membered)heteroaryl unsubstituted or substituted with (C1-C6)alkyl or (C6-C30)aryl; a (C6-C30)aryl unsubstituted or substituted with cyano, (3- to 30-membered)heteroaryl, or mono- or di- (C6-C30)arylamino; a tri(C1-C30)alkylsilyl; a tri(C6-C30)arylsilyl; a di(C1-C30)alkyl(C6-C30)arylsilyl; a (C1-C30)alkyldi(C6-C30)arylsilyl; an amino; a mono- or di- (C1-C30)alkylamino; a mono- or di- (C6-C30)arylamino; a (C1-C30)alkyl(C6-C30)arylamino; a (C1-C30)alkylcarbonyl; a (C1-C30)alkoxycarbonyl; a (C6-C30)arylcarbonyl; a di(C6-C30)arylboronyl; a di(C1-C30)alkylboronyl; a (C1-C30)alkyl(C6-C30)arylboronyl; a (C6-C30)aryl(C1-C30)alkyl; and a (C1-C30)alkyl(C6-C30)aryl; preferably, each independently, are at least one selected from the group consisting of a (C1-C6)alkyl; a (C6-C30)aryl unsubstituted or substituted with (3- to 30-membered)heteroaryl or di(C6-C30)arylamino; a (3- to 30-membered)heteroaryl unsubstituted or substituted with (C1-C6)alkyl or (C6-C30)aryl; and a mono- or di- (C6-C30)arylamino; or are linked to an adjacent substituent(s) to form a substituted or unsubstituted, mono- or polycyclic, (C5-C30) alicyclic or aromatic ring, whose carbon atom(s) may be replaced with at least one heteroatom selected from nitrogen, oxygen, and sulfur; and for example, an unsubstituted methyl, a phenyl unsubstituted or substituted with carbazolyl or diphenylamino, an unsubstituted biphenyl, an unsubstiuted naphthyl, a fluorenyl substituted with methyl, a benzofluorenyl substituted with methyl, an unsubstituted a dibenzothiophenyl, a carbazolyl unsubstituted or substituted with phenyl, a benzocarbazolyl unsubstituted or substituted with phenyl, an unsubstituted dibenzocarbazolyl, a pyrimidinyl substituted with phenyl, an unsubstituted benzonaphthothiophenyl, or an unsubstituted di(C6-C12)arylamino, or are linked to an adjacent substitutent(s) to form an indole ring substituted with phenyl, a benzoindole ring substituted with phenyl, an unsubstituted benzene ring, a benzindene ring substituted with methyl, or an indene ring substituted with methyl.
The organic electroluminescent compound represented by formula 1 includes the following compounds, but is not limited thereto:
Figure PCTKR2016006853-appb-I000005
Figure PCTKR2016006853-appb-I000006
Figure PCTKR2016006853-appb-I000007
Figure PCTKR2016006853-appb-I000008
Figure PCTKR2016006853-appb-I000009
Figure PCTKR2016006853-appb-I000010
Figure PCTKR2016006853-appb-I000011
Figure PCTKR2016006853-appb-I000012
Figure PCTKR2016006853-appb-I000013
Figure PCTKR2016006853-appb-I000014
Figure PCTKR2016006853-appb-I000015
Figure PCTKR2016006853-appb-I000016
Figure PCTKR2016006853-appb-I000017
Figure PCTKR2016006853-appb-I000018
Figure PCTKR2016006853-appb-I000019
Figure PCTKR2016006853-appb-I000020
Figure PCTKR2016006853-appb-I000021
Figure PCTKR2016006853-appb-I000022
The present disclosure further provides an organic electroluminescent material comprising the organic electroluminescent compound of formula 1, and an organic electroluminescent device comprising the organic electroluminescent material.
The organic electroluminescent material can be comprised of the organic electroluminescent compound of the present disclosure alone, or can further include conventional materials generally used in organic electroluminescent materials.
The organic electroluminescent device of the present disclosure may comprise a first electrode, a second electrode, and at least one organic layer between the first and second electrodes. The organic layer may comprise at least one organic electroluminescent compound of formula 1.
One of the first and second electrodes may be an anode, and the other may be a cathode. The organic layer may comprise a light-emitting layer, and may further comprise at least one layer selected from a hole injection layer, a hole transport layer, an electron transport layer, an electron buffer layer, an electron injection layer, an interlayer, a hole blocking layer, and an electron blocking layer.
The organic electroluminescent compound of formula 1 of the present disclosure can be comprised in the light-emitting layer as a host material or in an electron buffer layer. Preferably, the light-emitting layer may comprise at least one dopant. If necessary, another compound besides the organic electroluminescent compound of formula 1 may be comprised as a second host material.
Another embodiment of the present disclosure provides an electron buffer material comprising the organic electroluminescent compound of formula 1, and an organic electroluminescent device comprising the electron buffer material.
The organic electroluminescent device of the present disclosure comprises a first electrode; a second electrode opposing the first electrode; a light-emitting layer between the first electrode and the second electrode; and an electron transport zone and an electron buffer layer between the light-emitting layer and the second electrode. The electron buffer layer may comprise a compound represented by formula 1. When using the above compound, the driving voltage, the efficiency, and the lifespan of the device can be improved.
The dopant used in the present disclosure is preferably at least one phosphorescent dopant. The phosphorescent dopant material used for the organic electroluminescent device of the present disclosure is not limited, but may be preferably selected from metallated complex compounds of iridium (Ir), osmium (Os), copper (Cu), and platinum (Pt), more preferably selected from ortho-metallated complex compounds of iridium (Ir), osmium (Os), copper (Cu), and platinum (Pt), and even more preferably ortho-metallated iridium complex compounds.
The dopant to be comprised in the organic electroluminescent device of the present disclosure may be selected from the group consisting of the compounds represented by the following formulae 10 to 12.
Figure PCTKR2016006853-appb-I000023
wherein Ld is selected from the following structures:
Figure PCTKR2016006853-appb-I000024
R100 represents hydrogen, a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C3-C30)cycloalkyl;
R101 to R109 and R111 to R123, each independently, represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C3-C30)cycloalkyl, a cyano, or a substituted or unsubstituted (C1-C30)alkoxy; and adjacent substituents of R120 to R123 may be linked to each other to form a substituted or unsubstituted fused ring, e.g., a substituted or unsubstituted quinoline;
R124 to R127, each independently, represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C6-C30)aryl; and adjacent substituents of R124 to R127 may be linked to each other to form a substituted or unsubstituted fused ring, e.g., a substituted or unsubstituted fluorene, a substituted or unsubstituted dibenzothiophene, or a substituted or unsubstituted dibenzofuran;
R201 to R211, each independently, represent hydrogen, deuterium, a halogen, a substituted or unsubstituted a (C1-C30)alkyl, a substituted or unsubstituted (C3-C30)cycloalkyl, or a substituted or unsubstituted (C6-C30)aryl; and adjacent substituents of R201 to R211 may be linked to each other to form a substituted or unsubstituted fused ring, e.g., a substituted or unsubstituted dibenzofuran, or a substituted or unsubstituted dibenzothiophene;
r and s, each independently, represent an integer of 1 to 3; where r or s is an integer of 2 or more, each of R100 may be the same or different; and
t represents an integer of 1 to 3.
Specifically, the phosphorescent dopant materials include the following:
Figure PCTKR2016006853-appb-I000025
Figure PCTKR2016006853-appb-I000026
Figure PCTKR2016006853-appb-I000027
Figure PCTKR2016006853-appb-I000028
Figure PCTKR2016006853-appb-I000029
Figure PCTKR2016006853-appb-I000030
Figure PCTKR2016006853-appb-I000031
Figure PCTKR2016006853-appb-I000032
Figure PCTKR2016006853-appb-I000033
Figure PCTKR2016006853-appb-I000034
Figure PCTKR2016006853-appb-I000035
Figure PCTKR2016006853-appb-I000036
Figure PCTKR2016006853-appb-I000037
Figure PCTKR2016006853-appb-I000038
Figure PCTKR2016006853-appb-I000039
Figure PCTKR2016006853-appb-I000040
Figure PCTKR2016006853-appb-I000041
Figure PCTKR2016006853-appb-I000042
Figure PCTKR2016006853-appb-I000043
Figure PCTKR2016006853-appb-I000044
Figure PCTKR2016006853-appb-I000045
Figure PCTKR2016006853-appb-I000046
Figure PCTKR2016006853-appb-I000047
Figure PCTKR2016006853-appb-I000049
The organic electroluminescent device of the present disclosure may further comprise, in addition to the compound of formula 1, at least one compound selected from the group consisting of arylamine-based compounds and styrylarylamine-based compounds.
In the organic electroluminescent device of the present disclosure, the organic layer may further comprise, in addition to the compound of formula 1, at least one metal selected from the group consisting of metals of Group 1, metals of Group 2, transition metals of the 4th period, transition metals of the 5th period, lanthanides, and organic metals of the d-transition elements of the Periodic Table, or at least one complex compound comprising the metal. The organic layer may further comprise one or more additional light-emitting layers and a charge generating layer.
In addition, the organic electroluminescent device of the present disclosure may emit white light by further comprising at least one light-emitting layer, which comprises a blue, a red, or a green electroluminescent compound known in the field, besides the compound of the present disclosure. If necessary, it may further comprise a yellow or an orange light-emitting layer.
In the organic electroluminescent device of the present disclosure, preferably, at least one layer (hereinafter, "a surface layer”) may be placed on an inner surface(s) of one or both electrode(s), selected from a chalcogenide layer, a metal halide layer, and a metal oxide layer. Specifically, a chalcogenide (includes oxides) layer of silicon or aluminum is preferably placed on an anode surface of an electroluminescent medium layer, and a metal halide layer or a metal oxide layer is preferably placed on a cathode surface of an electroluminescent medium layer. Such a surface layer provides operation stability for the organic electroluminescent device. Preferably, the chalcogenide includes SiOX(1≤X≤2), AlOX(1≤X≤1.5), SiON, SiAlON, etc.; the metal halide includes LiF, MgF2, CaF2, a rare earth metal fluoride, etc.; and the metal oxide includes Cs2O, Li2O, MgO, SrO, BaO, CaO, etc.
In the organic electroluminescent device of the present disclosure, a mixed region of an electron transport compound and a reductive dopant, or a mixed region of a hole transport compound and an oxidative dopant may be placed on at least one surface of a pair of electrodes. In this case, the electron transport compound is reduced to an anion, and thus it becomes easier to inject and transport electrons from the mixed region to an electroluminescent medium. Furthermore, the hole transport compound is oxidized to a cation, and thus it becomes easier to inject and transport holes from the mixed region to the electroluminescent medium. Preferably, the oxidative dopant includes various Lewis acids and acceptor compounds, and the reductive dopant includes alkali metals, alkali metal compounds, alkaline earth metals, rare-earth metals, and mixtures thereof. A reductive dopant layer may be employed as a charge generating layer to prepare an electroluminescent device having two or more light-emitting layers and emitting white light.
In order to form each layer of the organic electroluminescent device of the present disclosure, dry film-forming methods such as vacuum evaporation, sputtering, plasma, and ion plating methods, or wet film-forming methods such as ink jet printing, nozzle printing, slot coating, spin coating, dip coating, and flow coating methods can be used.
When using a wet film-forming method, a thin film can be formed by dissolving or diffusing materials forming each layer into any suitable solvent such as ethanol, chloroform, tetrahydrofuran, dioxane, etc. The solvent can be any solvent where the materials forming each layer can be dissolved or diffused, and where there are no problems in film-formation capability.
Hereinafter, the organic electroluminescent compounds of the present disclosure, the preparation method thereof, and the properties of the device comprising the compounds will be explained in detail with reference to the representative compounds of the present disclosure.
Example 1: Preparation of compound C-24
Figure PCTKR2016006853-appb-I000050
1) Preparation of compound 1-1
After introducing compound A (CAS: 1044146-16-8, 36 g, 124 mmol), 4-chloro-2-formylbenzene boronic acid (25.2 g, 136 mmol), tetrakis(triphenylphosphine)palladium (5.7 g, 5.0 mmol), sodium carbonate (33 g, 150 mmol), toluene (600 mL), ethanol (150 mL), and distilled water (150 mL) into a reaction vessel, the mixture was stirred for 3 hours at 140°C. After completing the reaction, the precipitated solid was washed with distilled water and methanol. The obtained compound 1-1 was used in the next reaction without any further purification.
2) Preparation of compound 1-2
After introducing compound 1-1 (45.6 g, 130 mmol), (methoxymethyl)triphenylphosphonium chloride (74.3 g, 217 mmol), and tetrahydrofuran (1500 mL) into a reaction vessel, the mixture was stirred for 5 minutes. Potassium tert-butoxide (1M in THF, 220 mL) was then slowly added dropwise to the mixture at 0°C. The temperature of the mixture was slowly raised, and the mixture was stirred at room temperature for 3 hours. After completing the reaction by adding distilled water to the reaction solution, an organic layer was extracted with ethyl acetate. The extracted organic layer was dried with magnesium sulfate, and the solvent was removed therefrom using a rotary evaporator. Thereafter, the remaining product was purified by column chromatography to obtain compound 1-2 (48 g, 97 %).
3) Preparation of compound 1-3
After introducing compound 1-2 (44.8 g, 119 mmol), Eaton's reagent (4.5 mL), and chlorobenzene (600 mL) into a reaction vessel, the mixture was refluxed for 2 hours. After completing the reaction, the mixture was cooled to room temperature, and an organic layer was extracted with methylene chloride (MC). After drying the extracted organic layer with magnesium sulfate, the solvent was removed by using a rotary evaporator. Thereafter, the obtained product was purified by column chromatography to obtain compound 1-3 (36.3 g, 89 %).
4) Preparation of compound C-24
After introducing compound 1-3 (8 g, 23 mmol), compound B (CAS: 1060735-14-9, 9.5 g, 23 mmol), tris(dibenzylidyneacetone)dipalladium (1 g, 1.16 mmol), 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (s-phos) (0.95 g, 2.31 mmol), sodium tert-butoxide (4.5 g, 46.3 mmol), and o-xylene (150 mL) into a reaction vessel, the mixture was stirred for 3 hours at 170°C. After completing the reaction, the mixture was added dropwise to methanol, and the obtained solid was filtered. The obtained solid was purified by column chromatography to obtain compound C-24 (8.7 g, 68 %).
Example 2: Preparation of compound C-1
1) Preparation of compound 2-1
After introducing compound C (10 g, 29 mmol), bis(pinacolato)diborane (8.8 g, 34.8 mmol), tris(dibenzylidyneacetone)dipalladium (1.3 g, 1.45 mmol), 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (s-phos) (1.2 g, 2.9 mmol), potassium acetate (8.5 g, 87 mmol), and 1,4-dioxane (150 mL) into a reaction vessel, the mixture was stirred for 3 hours at 140°C. After completing the reaction, the mixture was cooled to room temperature, and an organic layer was extracted with ethyl acetate. After drying the extracted organic layer with magnesium sulfate, the solvent was removed by using a rotary evaporator. Thereafter, the obtained product was purified by column chromatography to obtain compound 2-1 (10.4 g, 82 %).
2) Preparation of compound C-1
After introducing compound 2-1 (10 g, 23.8 mmol), 2-chloro-4,6-diphenyltriazine (CAS: 3842-55-5, 6.4 g, 23.8 mmol), tris(dibenzylidyneacetone)dipalladium (1 g, 1.16 mmol), 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (s-phos) (1 g, 2.31 mmol), sodium tert-butoxide (4.5 g, 46.3 mmol), and o-xylene (150 mL) into a reaction vessel, the mixture was stirred for 3 hours at 170°C. After completing the reaction, the mixture was added dropwise to methanol, and the obtained solid was filtered. The obtained solid was purified by column chromatography to obtain compound C-1 (8.2 g, 55 %).
Example 3: Preparation of compound C-17
Figure PCTKR2016006853-appb-I000052
After introducing compound C (8 g, 23.1 mmol), compound D (CAS: 1448296-00-1, 7.7 g, 23.1 mmol), tetrakis(triphenylphosphine)palladium (1.4 g, 1.19 mmol), potassium carbonate (8.2 g, 60 mmol), toluene (90 mL), ethanol (30 mL), and distilled water (30 mL) into a reaction vessel, the mixture was stirred for 3 hours at 140°C. After completing the reaction, the precipitated solid was washed with distilled water and methanol. The obtained compound was purified by column chromatography to obtain compound C-17 (8.7 g, 77 %).
Example 4: Preparation of compound C-39
Figure PCTKR2016006853-appb-I000053
1) Preparation of compound 3-1
After introducing compound E (CAS: 913835-76-4, 40 g, 212.7 mmol), benzaldehyde (27 g, 255.29 mmol), sodium cyanide (10.4 g, 212.7 mmol), and N,N-dimethylformamide (DMF) (1000 mL) into a reaction vessel, the mixture was stirred for 3 hours at 100°C. The reaction solution cooled to room temperature was extracted with ethyl acetate. The obtained compound 3-1 was used in the next reaction without any further purification.
2) Preparation of compound 3-2
After introducing compound 3-1 (35 g, 128 mmol), 4-chloro-2-formylbenzene boronic acid (26 g, 141 mmol), tetrakis(triphenylphosphine)palladium (6 g, 5.1 mmol), sodium carbonate (34 g, 320 mmol), toluene (600 mL), ethanol (150 mL), and distilled water (150 mL) into a reaction vessel, the mixture was stirred for 3 hours at 140°C. After completing the reaction, the precipitated solid was washed with distilled water and methanol. The obtained compound 3-2 was used in the next reaction without further purification.
3) Preparation of compound 3-3
After introducing compound 3-2 (19 g, 56.9 mmol), (methoxymethyl)triphenylphosphonium chloride (29.3 g, 85.4 mmol), and tetrahydrofuran (500 mL) into a reaction vessel, the mixture was stirred for 5 minutes. Potassium tert-butoxide (1M in THF, 85 mL) was then slowly added dropwise to the mixture at 0°C. The temperature of the mixture was slowly raised, and the mixture was stirred at room temperature for 3 hours. After completing the reaction by adding distilled water to the reaction solution, an organic layer was extracted with ethyl acetate. The obtained organic layer was dried with magnesium sulfate, and the solvent was removed therefrom using a rotary evaporator. Thereafter, the remaining product was purified by column chromatography to obtain compound 3-3 (16.4 g, 80 %).
4) Preparation of compound 3-4
After introducing compound 3-3 (14.4 g, 39.8 mmol), Eaton's reagent (1.4 mL), and chlorobenzene (200 mL) into a reaction vessel, the mixture was refluxed for 2 hours. After completing the reaction, the mixture was cooled to room temperature, and an organic layer was extracted with methylene chloride (MC). After drying the extracted organic layer with magnesium sulfate, the solvent was removed by using a rotary evaporator. Thereafter, the obtained product was purified by column chromatography to obtain compound 3-4 (11.1 g, 79 %).
5) Preparation of compound C-39
After introducing compound 3-4 (4 g, 12.1 mmol), compound B (CAS: 1060735-14-9, 4.9 g, 12.1 mmol), tris(dibenzylidyneacetone)dipalladium (0.5 g, 0.61 mmol), 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (s-phos) (0.5 g, 1.21 mmol), sodium tert-butoxide (2.33 g, 24.3 mmol), and o-xylene (100 mL) into a reaction vessel, the mixture was stirred for 3 hours at 170°C. After completing the reaction, the mixture was added dropwise to methanol, and the obtained solid was filtered. The obtained solid was purified by column chromatography to obtain compound C-39 (8.7 g, 47 %).
Example 5: Preparation of compound C-49
Figure PCTKR2016006853-appb-I000054
1) Preparation of compound 2-1
Compound 2-1 was prepared in the same manner as described in Example 2.
2) Preparation of compound C-49
After introducing compound 2-1 (4.5 g, 10 mmol), 2-chloro-4,6-diphenylpyrimidine (CAS: 2915-16-4, 2.7 g, 10 mmol), tetrakis(triphenylphosphine)palladium (0.47 g, 0.4 mmol), potassium carbonate (3.6 g, 26 mmol), toluene (50 mL), ethanol (13 mL), and distilled water (13 mL) into a reaction vessel, the mixture was stirred for 4 hours at 120°C. After completing the reaction, the mixture was added dropwise to methanol, and the obtained solid was filtered. The obtained solid was purified by column chromatography to obtain compound C-49 (4.5 g, 73 %).
Example 6: Preparation of compound C-75
Figure PCTKR2016006853-appb-I000055
1) Preparation of compound 4-1
After introducing compound F (7.2 g, 21.8 mmol), bis(pinacolato)diborane (6.6 g, 26.2 mmol), tris(dibenzylidyneacetone)dipalladium (1.0 g, 1.1 mmol), 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (s-phos) (0.89 g, 2.2 mmol), potassium acetate (6.4 g, 65 mmol), and 1,4-dioxane (150 mL) into a reaction vessel, the mixture was stirred for 3 hours at 140°C. After completing the reaction, the mixture was cooled to room temperature, and an organic layer was extracted with ethyl acetate. After drying the extracted organic layer with magnesium sulfate, the solvent was removed by using a rotary evaporator. Thereafter, the obtained product was purified by column chromatography to obtain compound 4-1 (5.2 g, 57 %).
2) Preparation of compound C-75
After introducing compound 4-1 (5.2 g, 12.3 mmol), 2-chloro-4,6-diphenylpyrimidine (CAS: 2915-16-4, 3.3 g, 12.3 mmol), tetrakis(triphenylphosphine)palladium (0.71 g, 0.62 mmol), potassium carbonate (4.2 g, 30 mmol), toluene (60 mL), ethanol (20 mL), and distilled water (20 mL) into a reaction vessel, the mixture was stirred for 4 hours at 120°C. After completing the reaction, the mixture was added dropwise to methanol, and the obtained solid was filtered. The obtained solid was purified by column chromatography and recrystallization to obtain compound C-75 (5.3 g, 82 %).
Example 7: Preparation of compound C-87
Figure PCTKR2016006853-appb-I000056
1) Preparation of compound G
Compound G was prepared in the same manner as the preparation of compound 3-2 described in Example 4, except for using 5-chloro-2-formylboronic acid instead of 4-chloro-2-formylbenzene boronic acid.
2) Preparation of compound 5-1
After introducing compound G (15 g, 45.5 mmol), bis(pinacolato)diborane (13.9 g, 54.6 mmol), tris(dibenzylidyneacetone)dipalladium (1.6 g, 1.8 mmol), 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (s-phos) (0.9 g, 3.64 mmol), potassium acetate (13 g, 136 mmol), and 1,4-dioxane (350 mL) into a reaction vessel, the mixture was stirred for 3 hours at 140°C. After completing the reaction, the mixture was cooled to room temperature, and an organic layer was extracted with ethyl acetate. After drying the extracted organic layer with magnesium sulfate, the solvent was removed by using a rotary evaporator. Thereafter, the obtained product was purified by column chromatography to obtain compound 5-1 (20 g, 99 %).
3) Preparation of compound C-87
After introducing compound 5-1 (10 g, 22.7 mmol), 2-chloro-4,6-diphenylpyrimidine (CAS: 2915-16-4, 5.5 g, 20.6 mmol), tetrakis(triphenylphosphine)palladium (1.2 g, 1.0 mmol), potassium carbonate (7.1 g, 56 mmol), toluene (90 mL), ethanol (30 mL), and distilled water (30 mL) into a reaction vessel, the mixture was stirred for 4 hours at 120°C. After completing the reaction, the mixture was added dropwise to methanol, and the obtained solid was filtered. The obtained solid was purified by column chromatography and recrystallization to obtain compound C-87 (5.5 g, 51 %).
Example 8: Preparation of compound C-88
Figure PCTKR2016006853-appb-I000057
After introducing compound 5-1 (10 g, 23.7 mmol), 2-chloro-4,6-diphenyltriazine (CAS: 3842-55-5, 5.8 g, 21.6 mmol), tetrakis(triphenylphosphine)palladium (1.2 g, 1.0 mmol), potassium carbonate (7.5 g, 59 mmol), toluene (90 mL), ethanol (30 mL), and distilled water (30 mL) into a reaction vessel, the mixture was stirred for 4 hours at 120°C. After completing the reaction, the mixture was added dropwise to methanol, and the obtained solid was filtered. The obtained solid was purified by column chromatography and recrystallization to obtain compound C-88 (5.7 g, 50 %).
Example 9: Preparation of compound C-45
Figure PCTKR2016006853-appb-I000058
1) Preparation of compound 9-1
After introducing compound 7-bromo-2-phenyl-benzoxazole (37 g, 135 mmol), 4-chloro-2-formylbenzene boronic acid (25 g, 135 mmol), tetrakis(triphenylphosphine)palladium (7.8 g, 6.7 mmol), sodium carbonate (35 g, 338 mmol), toluene (680 mL), ethanol (170 mL), and distilled water (170 mL) into a reaction vessel, the mixture was stirred for 3 hours at 130°C. After completing the reaction, the precipitated solid was washed with distilled water and methanol. The obtained compound was purified by column chromatography to obtain compound 9-1 (26 g, 60 %).
2) Preparation of compound 9-2
After introducing compound 9-1 (26 g, 80.2 mmol), (methoxymethyl)triphenylphosphonium chloride (41 g, 120 mmol), and tetrahydrofuran (800 mL) into a reaction vessel, the mixture was stirred for 5 minutes. Potassium tert-butoxide (1M in THF, 120 mL) was then slowly added dropwise to the mixture at 0°C. The temperature of the mixture was slowly raised, and the mixture was stirred at room temperature for 3 hours. After completing the reaction by adding distilled water to the reaction solution, an organic layer was extracted with ethyl acetate. The extracted organic layer was dried with magnesium sulfate, and the solvent was removed therefrom using a rotary evaporator. Thereafter, the remaining product was purified by column chromatography to obtain compound 9-2 (25 g, 87 %).
3) Preparation of compound 9-3
After introducing compound 9-2 (25 g, 70.2 mmol), Eaton's reagent (3 mL), and chlorobenzene (350 mL) into a reaction vessel, the mixture was refluxed for 2 hours. After completing the reaction, the mixture was cooled to room temperature, and an organic layer was extracted with methylene chloride (MC). After drying the extracted organic layer with magnesium sulfate, the solvent was removed by using a rotary evaporator. Thereafter, the obtained product was purified by column chromatography to obtain compound 9-3 (13 g, 56 %).
4) Preparation of compound 9-4
After introducing compound 9-3 (13 g, 39 mmol), bis(pinacolato)dibororane (12 g, 47 mmol), tris(dibenzylidyneacetone)dipalladium (1.8 g, 1.9 mmol), 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (s-phos) (1.6 g, 3.9 mmol), potassium acetate (11 g, 118 mmol), and 1,4-dioxane (330 mL) into a reaction vessel, the mixture was stirred for 4 hours at 130°C. After completing the reaction, the mixture was cooled to room temperature, and an organic layer was extracted with ethyl acetate. After drying the extracted organic layer with magnesium sulfate, the solvent was removed by using a rotary evaporator. Thereafter, the obtained product was purified by column chromatography to obtain compound 9-4 (13 g, 81 %).
5) Preparation of compound C-45
After introducing compound 9-4 (13 g, 31 mmol), 2-chloro-4,6-diphenyltriazine (8 g, 30 mmol), tetrakis(triphenylphosphine)palladium (1.7 g, 1.5 mmol), potassium carbonate (10 g, 75 mmol), toluene (140 mL), ethanol (35 mL), and distilled water (35 mL) into a reaction vessel, the mixture was stirred for 4 hours at 130°C. After completing the reaction, the precipitated solid was washed with distilled water and methanol. Thereafter, the obtained product was purified by column chromatography to obtain compound C-45 (7.7 g, 49 %).
Example 10: Preparation of compound C-100
Figure PCTKR2016006853-appb-I000059
After introducing compound 9-4 (3 g, 7.1 mmol), 2-(3-bromophenyl)-4,6-diphenyl-1,3,5-triazine (CAS: 864377-31-1, 3.04 g, 7.8 mmol), tetrakis(triphenylphosphine)palladium (0.41 g, 0.36 mmol), sodium carbonate (1.9 g, 17.8 mmol), toluene (24 mL), ethanol (6 mL), and distilled water (6 mL) into a reaction vessel, the mixture was stirred for 4 hours at 120°C. After completing the reaction, the mixture was added dropwise to methanol, and the obtained solid was filtered. The obtained solid was purified by column chromatography and recrystallization to obtain compound C-100 (2.3 g, 54 %).
Example 11: Preparation of compound C-101
Figure PCTKR2016006853-appb-I000060
After introducing compound 9-4 (3.48 g, 8.3 mmol), 2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine (CAS: 1472062-94-4, 3.53 g, 9.1 mmol), tetrakis(triphenylphosphine)palladium (0.48 g, 0.41 mmol), sodium carbonate (2.2 g, 20.7 mmol), toluene (28 mL), ethanol (7 mL), and distilled water (7 mL) into a reaction vessel, the mixture was stirred for 5 hours at 120°C. After completing the reaction, the mixture was added dropwise to methanol, and the obtained solid was filtered. The obtained solid was purified by column chromatography and recrystallization to obtain compound C-101 (3.7 g, 74 %).
The properties of the above synthesized compounds are shown in Table 1 below.
Figure PCTKR2016006853-appb-I000061
Hereinafter, the luminescent properties of the organic electroluminescent device comprising the organic electroluminescent compound of the present disclosure will be explained in detail with reference to the following examples.
Device Example 1: Preparation of an OLED device comprising the organic
electroluminescent compounds of the present disclosure as a host
An OLED device was produced by using the organic electroluminescent compound according to the present disclosure. A transparent electrode indium tin oxide (ITO) thin film (10 Ω/sq) on a glass substrate for an organic light-emitting diode (OLED) device (Geomatec) was subjected to an ultrasonic washing with acetone, ethanol, and distilled water, sequentially, and then was stored in isopropanol. The ITO substrate was then mounted on a substrate holder of a vacuum vapor depositing apparatus. Compound HI-1 was introduced into a cell of said vacuum vapor depositing apparatus, and then the pressure in the chamber of said apparatus was controlled to 10-6 torr. Thereafter, an electric current was applied to the cell to evaporate the above-introduced material, thereby forming a first hole injection layer having a thickness of 80 nm on the ITO substrate. Next, compound HI-2 was introduced into another cell of said vacuum vapor depositing apparatus, and was evaporated by applying an electric current to the cell, thereby forming a second hole injection layer having a thickness of 5 nm on the first hole injection layer. Compound HT-1 was then introduced into the cell of said vacuum vapor depositing apparatus, and was evaporated by applying an electric current to the cell, thereby forming a first hole transport layer having a thickness of 10 nm on the second hole injection layer. Compound HT-3 was then introduced into another cell of said vacuum vapor depositing apparatus, and was evaporated by applying an electric current to the cell, thereby forming a second hole transport layer having a thickness of 60 nm on the first hole transport layer. After forming the hole injection layer and the hole transport layer, a light-emitting layer was formed thereon as follows: compound C-24 was introduced into one cell of said vacuum vapor depositing apparatus as a host, and compound D-71 was introduced into another cell as a dopant. The dopant was deposited in a doping amount of 3 wt% based on the total amount of the host and dopant to form a light-emitting layer having a thickness of 40 nm on the second hole transport layer. Compound ET-1 and compound EI-1 were then introduced into another two cells, and evaporated at a rate of 1:1 to form an electron transport layer having a thickness of 30 nm on the light-emitting layer. After depositing compound EI-1 as an electron injection layer having a thickness of 2 nm on the electron transport layer, an Al cathode having a thickness of 80 nm was deposited by another vacuum vapor deposition apparatus. Thus, an OLED device was produced.
Figure PCTKR2016006853-appb-I000062
The produced OLED device showed a red emission having a luminance of 1,000 cd/m2, and a luminous efficiency of 24.4 cd/A at 4.4 V. The time taken to be reduced to 90% of the luminance, where the early luminance is 100%, at 5,000 nits and a constant current was 43 hours or more.
Device Example 2: Preparation of an OLED device comprising the organic
electroluminescent compounds of the present disclosure as a host
An OLED device was produced in the same manner as in Device Example 1, except for using compound C-1 as a host of the light-emitting material. The produced OLED device showed a red emission having a luminance of 1,000 cd/m2, and a luminous efficiency of 27.8 cd/A at 6.0 V. The time taken to be reduced to 90% of the luminance, where the early luminance is 100%, at 5,000 nits and a constant current was 37 hours or more.
Device Example 3: Preparation of an OLED device comprising the organic
electroluminescent compounds of the present disclosure as a host
An OLED device was produced in the same manner as in Device Example 1, except for using the compound C-39 as a host of the light-emitting material. The produced OLED device showed a red emission having a luminance of 1,000 cd/m2, and a luminous efficiency of 22.9 cd/A at 4.5 V. The time taken to be reduced to 90% of the luminance, where the early luminance is 100%, at 5,000 nits and a constant current was 38 hours or more.
Comparative Device Example 1: Preparation of an OLED device comprising
conventional organic electroluminescent compounds
An OLED device was produced in the same manner as in Device Example 1, except for using the following compound K as a host of the light-emitting material.
Figure PCTKR2016006853-appb-I000063
The produced OLED device showed a red emission having a luminance of 1,000 cd/m2, and a luminous efficiency of 14.3 cd/A at 10.0 V. The time taken to be reduced to 90% of the luminance, where the early luminance is 100%, at 5,000 nits and a constant current was less than 1 hour.

Claims (6)

  1. An organic electroluminescent compound represented by the following formula 1:
    Figure PCTKR2016006853-appb-I000064
    wherein
    X1 represents -N=, -NR7-, -O-, or -S-;
    Y1 represents -N=, -NR8-, -O-, or -S-;
    with the provisos that when X1 represents -N=, then Y1 represents -NR8-, -O-, or -S-, and when X1 represents -NR7-, then Y1 represents -N=, -O-, or -S-, with the provisos that X1 and Y1 are not simultaneously -O-; X1 and Y1 are not simultaneously -S-; X1 and Y1 are not -O- and -S-, respectively; and X1 and Y1 are not -S- and -O-, respectively;
    R1 represents a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered)heteroaryl;
    R2 to R4, R7, and R8, each independently, represent hydrogen, deuterium, a halogen, a cyano, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (3- to 30-membered)heteroaryl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C1-C30)alkoxy, a substituted or unsubstituted tri(C1-C30)alkylsilyl, a substituted or unsubstituted di(C1-C30)alkyl(C6-C30)arylsilyl, a substituted or unsubstituted (C1-C30)alkyldi(C6-C30)arylsilyl, a substituted or unsubstituted tri(C6-C30)arylsilyl, a substituted or unsubstituted mono- or di- (C1-C30)alkylamino, a substituted or unsubstituted mono- or di- (C6-C30)arylamino, or a substituted or unsubstituted (C1-C30)alkyl(C6-C30)arylamino; or are linked to an adjacent substituent(s) to form a substituted or unsubstituted, mono- or polycyclic, (C3-C30) alicyclic or aromatic ring, whose carbon atom(s) may be replaced with at least one heteroatom selected from nitrogen, oxygen, and sulfur;
    a represents 1; b and c, each independently, represent 1 or 2; d represents an integer of 1 to 4; and
    the heteroaryl contains at least one heteroatom selected from B, N, O, S, Si, and P.
  2. The organic electroluminescent compound according to claim 1, wherein formula 1 is represented by the following formula 2:
    Figure PCTKR2016006853-appb-I000065
    wherein
    L1 represents a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (3- to 30-membered)heteroarylene;
    X2 to X4, each independently, represent -N- or -CR9-;
    Ar1 and Ar2, each independently, represent a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered)heteroaryl;
    R9 has the same definition as R2 to R4;
    e represents an integer of 1 to 3; and
    X1, Y1, R1 to R4, a, b, and c are as defined in claim 1.
  3. The organic electroluminescent compound according to claim 1, wherein formula 1 is represented by the following formula 3:
    Figure PCTKR2016006853-appb-I000066
    wherein
    L1 represents a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (3- to 30-membered)heteroarylene;
    Z represents a single bond, or a substituted or unsubstituted (C1-C6)alkylene;
    R5 and R6, each independently, have the same definition as R2 to R4;
    n represents 0 or 1; e represents an integer of 1 to 3; f and g, each independently, represent an integer of 1 to 4; and
    X1, Y1, R1 to R4, a, b and c are as defined in claim 1.
  4. The organic electroluminescent compound according to claim 1, wherein formula 1 is represented by the following formula 4:
    Figure PCTKR2016006853-appb-I000067
    wherein
    L1 represents a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (3- to 30-membered)heteroarylene;
    Z represents a single bond, or a substituted or unsubstituted (C1-C6)alkylene;
    W represents -NR10-, -O-, -S-, or -CR11R12-;
    R10 represents a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered)heteroaryl;
    R11 and R12, each independently, represent a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered)heteroaryl;
    R5 and R6, each independently, have the same definition as R2 to R4;
    n represents 0 or 1; e and h, each independently, represent an integer of 1 to 3; g represents an integer of 1 to 4; and
    X1, Y1, R1 to R4, a, b and c are as defined in claim 1.
  5. The organic electroluminescent compound according to claim 1, wherein the compound represented by formula 1 is selected from the group consisting of:
    Figure PCTKR2016006853-appb-I000068
    Figure PCTKR2016006853-appb-I000069
    Figure PCTKR2016006853-appb-I000070
    Figure PCTKR2016006853-appb-I000071
    Figure PCTKR2016006853-appb-I000072
    Figure PCTKR2016006853-appb-I000073
    Figure PCTKR2016006853-appb-I000074
    Figure PCTKR2016006853-appb-I000075
    Figure PCTKR2016006853-appb-I000076
    Figure PCTKR2016006853-appb-I000077
    Figure PCTKR2016006853-appb-I000078
    Figure PCTKR2016006853-appb-I000079
    Figure PCTKR2016006853-appb-I000080
    Figure PCTKR2016006853-appb-I000081
    Figure PCTKR2016006853-appb-I000082
    Figure PCTKR2016006853-appb-I000083
    Figure PCTKR2016006853-appb-I000084
    Figure PCTKR2016006853-appb-I000085
  6. An organic electroluminescent device comprising the organic electroluminescent compound according to claim 1 as a host material.
PCT/KR2016/006853 2015-08-19 2016-06-27 Organic electroluminescent compounds and organic electroluminescent device comprising the same Ceased WO2017030283A1 (en)

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EP16837225.8A EP3344606B1 (en) 2015-08-19 2016-06-27 Organic electroluminescent compounds and organic electroluminescent device comprising the same
US17/558,910 US11807788B2 (en) 2015-08-19 2021-12-22 Organic electroluminescent compounds and organic electroluminescent device comprising the same
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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018151470A1 (en) * 2017-02-16 2018-08-23 Rohm And Haas Electronic Materials Korea Ltd. Organic electroluminescent compound and organic electroluminescent device comprising the same
WO2018155942A1 (en) * 2017-02-27 2018-08-30 Rohm And Haas Electronic Materials Korea Ltd. A plurality of host materials and organic electroluminescent device comprising the same
KR20180099487A (en) * 2017-02-27 2018-09-05 롬엔드하스전자재료코리아유한회사 A plurality of host materials and organic electroluminescent device comprising the same
CN111149229A (en) * 2017-09-22 2020-05-12 罗门哈斯电子材料韩国有限公司 Multiple host materials and organic electroluminescent device comprising the same
CN112292437A (en) * 2018-06-22 2021-01-29 罗门哈斯电子材料韩国有限公司 Organic electroluminescent compound, organic electroluminescent material, and organic electroluminescent device comprising same
US20210184133A1 (en) * 2019-12-16 2021-06-17 Rohm And Haas Electronic Materials Korea Ltd. Organic electroluminescent compound, a plurality of host materials, and organic electroluminescent device comprising the same
JP2021106258A (en) * 2019-12-26 2021-07-26 ローム・アンド・ハース・エレクトロニック・マテリアルズ・コリア・リミテッド Multiple host materials and organic electroluminescent device comprising the same
US20210257556A1 (en) * 2020-01-31 2021-08-19 Rohm And Haas Electronic Materials Korea Ltd. Organic electroluminescent compound, a plurality of host materials, and organic electroluminescent device comprising the same
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US20220251051A1 (en) * 2019-05-22 2022-08-11 Rohm And Haas Electronic Materials Korea Ltd. Organic electroluminescent compound and organic electroluminescent device thereof
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3279918A (en) * 1960-03-31 1966-10-18 Gevaert Photo Prod Nv Electrophotographic material
JP2001023777A (en) 1999-07-08 2001-01-26 Toray Ind Inc Luminescent element
WO2007095753A1 (en) 2006-02-24 2007-08-30 Merck Frosst Canada Ltd. 2-(phenyl or heterocyclic) - 1h-phenanthro [9,10-d] imidazoles
US20120168731A1 (en) 2009-06-18 2012-07-05 Basf Se Phenanthroazole compounds as hole transporting materials for electro luminescent devices

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3279918A (en) * 1960-03-31 1966-10-18 Gevaert Photo Prod Nv Electrophotographic material
JP2001023777A (en) 1999-07-08 2001-01-26 Toray Ind Inc Luminescent element
WO2007095753A1 (en) 2006-02-24 2007-08-30 Merck Frosst Canada Ltd. 2-(phenyl or heterocyclic) - 1h-phenanthro [9,10-d] imidazoles
US20120168731A1 (en) 2009-06-18 2012-07-05 Basf Se Phenanthroazole compounds as hole transporting materials for electro luminescent devices

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
APPL. PHYS. LETT., vol. 51, 1987, pages 913
AWAD, W. I. ET AL.: "Chrysenoxazoles", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 77, 1955, pages 1013 - 1014, XP055365835 *
AWAD, W. I. ET AL.: "Darzens reactions with quinonoid systems. Spiro Oxirane-2,2'- chrysenes from chrysenequinone, and chryso-oxazoles from chrysenequinone imine or chrysenequinone monoxime", JOURNAL FUER PRAKTISCHE CHEMIE, vol. 320, no. 6, 1978, pages 986 - 990, XP055365836 *
AWAD, W. I. ET AL.: "Infra-Red spectra of chrysenequinonimine and chrysenoxazoles", EGYPTIAN JOURNAL OF CHEMISTRY, vol. 1, no. 1, 1958, pages 87 - 98, XP009508772 *
CHEMICAL ABSTRACTS, Columbus, Ohio, US; abstract no. 1472062-94-4
OSMAN, A-M. ET AL.: "2-Arylnaphthoxazoles and some other condensed oxazoles", JOURNAL OF ORGANIC CHEMISTRY, vol. 27, 1961, pages 558 - 561, XP008136240 *
See also references of EP3344606A4

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